气相色谱-三重四极杆质谱联用技术检测土壤中卤代多环芳烃

Analysis of Halogenated Polycyclic Aromatic Hydrocarbons in Soil Samples Using Gas Chromatography Coupled with Triple Quadrupole Mass Spectrometry

  • 摘要: 卤代多环芳烃(halogenated polycyclic aromatic hydrocarbons, XPAHs)是多环芳烃的氯代或溴代衍生物,因具有神经毒性、致畸变性和致癌性等特性,近年来受到广泛关注。目前,在一些环境介质(如土壤)中的XPAHs水平和分布特征等研究不够充分,亟需发展分析检测的新方法和新技术。本研究建立了气相色谱三重四极杆质谱(gas chromatography coupled with triple quardrupole mass spectrometry, GC-MS/MS)法定性定量分析土壤中37种XPAHs同类物,探索了GC-MS/MS分析检测XPAHs的最佳参数条件,优化了土壤样品的前处理过程,并验证了方法的有效性。结果表明,方法的检出限为0.03~1.17 pg/g,回收率为43.7%~115%。对比GC-MS/MS与高分辨气相色谱-高分辨磁质谱(high resolution gas chromatography coupled with high resolution magnetic mass spectrometry, HRGC-HRMS)的检测结果发现,其准确度和灵敏度相当,能够满足环境样品中XPAHs的定量分析要求。采用该方法分析检测采自河北地区的5个土壤样品中XPAHs,其浓度范围为648~11 868 pg/g,低于此前报道的电子垃圾拆解地的土壤XPAHs水平(13.2~278 ng/g)。通过分析浓度水平和分布特征发现,土壤样品中XPAHs可能受周边工业生产等人类活动排放源的影响。

     

    Abstract: Halogenated polycyclic aromatic hydrocarbons (XPAHs) are chlorinated or brominated derivatives of polycyclic aromatic hydrocarbons. Due to their toxicities, such as neurotoxicity, deformability and carcinogenicity, and physicochemical properties, such as long-range transportation and semi-volatility, they are recognized as emerging pollutants, and have attracted widespread attention in recent years. Even though occurrence characteristics of XPAHs in some environmental matrices have been studied, such as air collected in Beijing and Japan, most of other environmental matrices have not been well studied, such as soil samples. Therefore, quick and effective analytical techniques and methods are necessary to be developed to fulfill the analytical requirements. In this study, a method of gas chromatography coupled with triple quardrupole mass spectrometry (GC-MS/MS) was established for qualification and quantitation of 37 XPAHs in soil samples. The operation parameters of gas chromatography and mass spectrometry were explored to achieve the best separation and detection of XPAHs, the pretreatment method was optimized, and the effectiveness of the analytical method was verified. The results showed that the detection limits of XPAHs were 0.03-1.17 pg/g, and recoveries were 43.7%-115%. Comparison of GC-MS/MS method established in this study and high-resolution gas chromatography coupled with high-resolution mass spectrometry (HRGC-HRMS) method established in our previous studies showed that both the accuracy and sensitivity were comparable. This indicated that the GC-MS/MS method could meet the quantitation requirement of XPAHs in soil samples. Finally, this method was applied to analyze XPAHs in soil samples collected from Hebei Province. The concentrations of XPAHs in the collected soil samples were 648-11 868 pg/g, lower than that in soil samples collected from e-waste dismantling sites (13.2-278 ng/g) reported in previous studies. The levels and distributions of XPAHs in the collected samples could be affected by the anthropogenic activity sources, such as industrial production and emissions around the sampling sites.

     

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